TWI248448B - Curing agent composition and curing epoxy resin composition - Google Patents

Abstract

A curing agent composition for an epoxy resin which comprises (B) a reaction product obtained from (a) a monoamine compound comprising an amine compound represented by formula (I), wherein R1 and R2 each represent an alkyl group having 1 to 8 carbon atoms, or R1 and R2 are connected together to form an alkylene group which may contain an oxygen atom or a nitrogen atom; and n represents 1 to 6, (b) a polyamine compound comprising a dicarboxylic acid dihydrazide, (c) an organic polyisocyanate, and, if desired, (d) an epoxy compound.

Description

1248448

V. INSTRUCTION DESCRIPTION OF THE INVENTION (1) BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin curable epoxy resin composition and a hardener composition for a lipid, which is composed of a combination of the epoxy resin: heating The hardened epoxy resin composition has good preservation stability, and = ιΐΓΓ:: more physicochemical properties, etc., and the single-liquid type heat-hardening work clothes oxygen tree 曰 曰 composition is sentenced s & oxidation character. , a hardening agent composition for a mouth-coating resin and a polycyclic ring [described in the related art] ring: the resin has good adhesion to various substrates, and in addition, the hardened product obtained by hardening the latex resin with a hardener is pure Good heat resistance, chemical resistance, == mechanical properties, etc., so it is used in a wide range of fields, especially in the field of coatings or adhesives. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives. The epoxy resin composition is used to add hardener and harden before use: the two-liquid type of the incoming agent is the mainstream. The two-liquid type is characterized in that it can be hardened at normal temperature or in a pan/dish. In other words, it must be metered and mixed before use. Further, it can be used for a short period of time, and it is difficult to apply it to an automatic machine. Restricted, this is its shortcoming. In order to eliminate the (four) problem, a single-liquid type curable epoxy resin composition is required. In order to obtain such a one-liquid type curable resin composition, a hardener is required which has a property of not reacting at room temperature, but can be hardened by heating to start the reaction, i.e., a latent hardener. The proposed latent hardeners are, for example, dichloro acetaminophen, dibasic acid dioxime, boron trifluoride amine complex -4- This paper scale applies to China-National Standard 1cns) a4 specification (10) χ^^ I7 1248448 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. Description of invention (2) Salt, guanamine, melamine, imidazole, etc. However, for example, the combination of -, -, -, - mercaptoamine, melamine, guanamine and epoxy resin has excellent storage stability, but the disadvantage is that it requires a high temperature of 15 〇Ό or more ^ Between ^ hardening conditions. Further, although the method of using these and the hardening accelerator together to shorten the hardening time is widely practiced, it adversely affects the storage stability. On the other hand, dibasic acid diindole and imidazole can harden at a lower temperature, but lack storage stability. Although the boron trifluoride amine complex salt has the advantages of good storage stability and short hardening time, it has disadvantages such as poor water resistance and corrosiveness to metals. In order to solve the above-mentioned problems, the reaction product of a dialkylamine and an epoxide is used as a reaction product of the dialkylamine and the epoxide in the Japanese Patent Laid-Open Publication No. SHO-56-155222 A polyepoxide hardener is used, and a reaction product of a third amino group alcohol or a phenol and a polyepoxide is used as a hardener of a polyepoxide in the Japanese Patent Laid-Open Publication No. SHO 53 526. use. However, the epoxy resin composition comprising the hardener composition is not sufficiently stored: the crucible is not an object which satisfies the physical properties of the hardened material. Further, a method of using a hardener compound obtained by heating a reaction of N,N-dialkylamine alkylamine, a cyclic amine, and an isocyanate is proposed in the Japanese Patent Laid-Open Publication No. Hei No. Hei. Store the stability of things. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a one-liquid type curable epoxy resin composition which has good storage stability and is excellent in hardenability, adhesion, and hardened material--- -------- (Please read the note on the back? Please fill out this page again) -5- 1248448

V. INSTRUCTIONS OF THE INVENTION (3) The physical properties of the present invention are excellent. The inventors of the present invention have continually concentrated on the results, and found that the use of N,N-alkylamine alkylamines, diacids and organic A polyhard isocyanate = a latent hardener to obtain a curable epoxy resin composition which can achieve the above object, and the present invention is completed. That is, the present invention provides a hardener composition for an epoxy resin. The second component consists of containing a reactant (B) which comprises a monoamine compound (a) comprising an amine compound of the general formula (I), comprising a bismuth dicarboxylate <polyamine Compound (b), organic polyisocyanate ((〇, and as needed epoxy compound (d) reaction: Dimensional, _ R2〆N^CH2^~NH2 (I) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative In the printing formula, 'R〗 and R 2 are each a carbon number of 丨8, or R1 and R2 are bonded to an alkyl group which may contain an oxygen atom or a nitrogen atom, and η is 1 to 6 The present invention further provides a hardener composition for an epoxy resin, which comprises a reactant (Β), and An epoxy adduct (c) of a compound obtained by a monoamine compound (a) comprising an amine compound of the general formula (丨), a polyamine compound comprising dioxonium dicarboxylate ( b), the organic polyisocyanate (c), and optionally the epoxy compound (d) are obtained. The present invention further provides a one-component heat-curable epoxy resin composition comprising a polyepoxy compound (A) And a hardener composition comprising a reactant (B), the reactant (B) comprising a monoamine compound (a) comprising one of the amine compounds of the general formula (I), Contains two --------- '装-------- order--------- turtle (please read the back of the note before you fill out this page) -6 - this paper The scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1248448

And polyamines containing diterpene bismuth phthalate. The material rrj is a single-component heat-curing epoxy resin combination and system. s polyepoxide (Α) and a hardener composition: the composition comprises a reactant (B), and an amine compound; the product (C), the reactant (B) is made to contain the table = The monoamine compound (4), which comprises a direxate di- bis (=), an organic polyisocyanate (0, and optionally (d) a reaction. The enamel compound of the present invention is a single epoxy resin composition. Liquid type and heat-hardenable, good stability, and hardenability, adhesion, and physical properties of the cured product are all described in detail. The following is a detailed description of the hardenable epoxy resin composition for curing epoxy resin of the invention. Regarding the monoamine compound (4) used in the present invention, the amine compound of the formula (1) is used as a lower amine compound, and can be further used in combination with other monoamines such as an amine or a ring. Hexylamine, etc. Ma Ben: NKCH^NH2 (I) ------------Package--------Book--------- (Please read the back Note: Please fill out this page again) In the printed version of the Ministry of Economic Affairs' Intellectual Property Bureau employee consumption cooperative, 1 and Han 2 are each a carbon number 8 alkyl, or R The 2 series is bonded to an alkyl group which may contain an oxygen atom or a nitrogen atom, and η is 1 to 6 j. In the above formula, the alkyl groups represented by Ri and R2 may be, for example, a methyl group, a propyl group or a butyl group. , pentyl, hexyl, heptyl, octyl and other bases,: -7- and B-paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1248448 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative System A7 V. Description of the invention (5^ and r2 may also be bonded to a (4) group which may contain an oxygen atom or a nitrogen atom, for example, =, R!, R2 and the nitrogen atom bonded thereto may form a morpholine ring a ring structure such as a piperidine ring or a piperazine ring. Such a group of the dialkylamine alkylamines of the general formula (1) may be, for example, N ice dimethylaminopropylamine or N,N-diethylamine. Propylamine, N,N_: propylaminopropylamine, n,n-dibutylaminopropylamine, N,N-:methylaminoethylamine, n,n-dimethylaminopropylamine, N,N-methylamine Butyramine, amine propyl morpholine, amine ethyl piperidine, 1-aminoethyl)-4-methyl benzylazine, etc. Regarding the polyamine compound (b) used in the present invention, Dicarboxylic acid dicarboxylic acid For example, it may be diammonium adipate: malonic acid, second brewing, succinic acid diterpene, glutaric acid di-n-bismuth, diammonium adipate, dicaptanic acid diterpene, sebacic acid diterpenoid In addition, the polyamine compound of the component (b) of the present invention may be a polyamine compound other than the dicarboxylic acid, and other polyamine compounds such as these may be used. It may be diethylenetriamine, triethylenetetramine 'tetraethylenepentamine, guanamine propane, guanidine diamine cyclohexane, oxime diamine _3,6-diethylcyclohexan, isophor (four) one Amine, m-xylylenediamine, diaminodiphenylmethane, diamine sulfone, piperazine, etc. ^ Α Here, in the case where the polyamine compound other than the di(tetra)difluorene is used as the component (b) The other materials are not more than 5 moles of other polyamine compounds, preferably no more than = ear, if the amount used exceeds this enthalpy, it is not good because of the preservation stability of pyridazole. ''8' This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -----------Install--------Book----- ----w&w (please read the notes on the back and fill out this page) 1248448 A7 B7 V. Inventions (6) Here, about the ratio of (a) ingredients to (b) ingredients, I am surprised The composition of (a) of 丨 丨 耳 , , 系 a a 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨It is not good for preserving stability and reducing various properties such as hardenability and adhesion. As the organic polyisocyanate (c) used in the present invention, it may be an aliphatic, alicyclic or aromatic polyisocyanate, specifically, bismuth, diisocyanate methylcyclohexane, 2,4_stretch Tolyl diisocyanate, 2, '6-extended phenyl diisocyanate, 4,4,-diphenylmethane diisocyanate, phenyl diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, Tetraded methyl diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, hydrazine, 4_cyclohexyl diisocyanate, 4,4,_dicyclohexylmethane diisocyanate, 3,3,_ Dimethoxy-4,4,_bis-phenylene diisobutyl, 1,5-extended tea diisocyanate, hydrazine, 5_tetrahydroethylene base diisocyanate, isophora diisocyanate, etc. . As regards the amount of the component (c) used, it is preferably used in combination with one of the sulfhydryl groups of the amine component of the component (b) and the iNC group of the component (c). The amount is 〇·5~1. If less than 〇1 is used, there is a 降 保存 保存 保存 保存 保存 保存 保存 保存 保存 保存 保存 保存 保存 保存 保存 吡 吡 吡 吡 吡 吡 吡 吡 吡 吡 吡 吡 吡 吡 吡 吡 吡 吡 吡 吡 吡 吡 吡 吡In addition, in the manufacture of the reactant (B) used in the present invention, the epoxy compound (d) can be used for epoxy modification, and the epoxy is modified. The compound may be, for example, the above polyepoxy compound such as bisphenol A, bisphenol F or the like polyglycidyl ether, diglycidyl aniline or diglycidyl o-toluidine; phenyl -9 - paper scale applicable to China Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the back and fill out this page) Binding · Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1248448 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed A7 Β7 V. Description of invention (7) Hydroglycidyl ether, tolyl shrinkage Monoepoxy compounds such as oleyl ether, butyl phenyl glycidyl ether, tetraglycidyl metaxylene diamine, etc. As for the amount of these (d) components, relative to one component.) The NH2 group of the amine compound is used in an amount of 〇·9 or less (epoxy group of the magic component, preferably in the range of 0.01 to 0.5), and when it is used in more than 〇·9, the curing property is lowered. In the hardener composition for epoxy resin of the present invention, the epoxy adduct (c) of the reactant (Β) and the amine compound can be used at the same time. The amine compound (e) of the oxygen adduct (c) preferably contains the amine compound of the above general formula (1). Further, other amine compounds may be used in combination, and such other amine compounds may be, for example, benzene. a monoamine such as methylamine or cyclohexylamine; diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,2-aminepropane, i,2-diaminocyclohexane, diamine... Diethylcyclohexane, isophoronediamine, m-xylylenediamine, diaminodiphenylcarbene, diaminodiphenyl reduction, An epoxy compound (f) which can provide an epoxy compound (c) of an amine compound, which can be exemplified by the above epoxy compound (d). Preferably, the Nh2 group of the amine compound (e) is an epoxy group having 0.5 to 2 epoxy compounds. When the hardener composition for an epoxy resin of the present invention is to be produced, it is not necessary to limit the preparation method. It can be easily produced by the following method: a method of mixing a monoamine compound (a) and a polyamine compound (b) in an organic falling agent, and slowly adding an organic polyisocyanate (c) thereto to cause a reaction Method (2) In the organic catalyzed agent, the mixed monoamine compound (a) and the polyamine compound -10- are used in the Ningguo National Standard (CNS) A4 specification (21〇χ 297 mm) ---- ------.装--------Book--------- (Please read the notes on the back and fill out this page) 1248448 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing A7 B7 V. Inventive Note (8) (b), in which the organic polyisocyanate (c) is slowly added, reacted, and then an amine compound is added. (e) and epoxy compound (f) to cause reaction; method (3) mixing monoamine compound (a) and polyamine compound (b) in an organic solvent to slowly add an epoxy compound (d) Further, the organic polyisocyanate (c) is gradually added thereto to cause a reaction, and the method (4) is carried out in an organic solvent, and the monoamine compound (a) and the polyamine compound (1) are mixed, and the organic compound is gradually added thereto. The polyisocyanate (c) is reacted, and the reactant obtained by reacting the amine compound (e) with the epoxy compound (f) is mixed. As the organic solvent which can be used herein, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate, cyclohexanone Ethers such as ketones, tetrahydrofuran, anthracene, 2-dimethoxyethane-1-ethoxyethyl ether, esters such as ethyl acetate and n-butyl acetate; ethers such as propylene glycol monomethyl ether acetate Esters; iso- or n-butanol, iso- or propanol, pentanol and other alcohols; aromatic hydrocarbons such as benzene, toluene, xylene; terpene hydrocarbons such as decanediol oil, D-quinone diterpene, terpene ; Olefin, Siwazelu #310 (Kos Mosson Mountain Petroleum (share)), Thorubeso #1〇〇 (Yeksson Chemical (share)) and other olefin-based solvents; four gasified carbon, gas An aliphatic hydrocarbon such as trichloroethylene or methylene chloride; an aromatic hydrocarbon such as chlorinated benzene; aniline, triethylamine, acridine, dioxane, acetic acid, acetonitrile, carbon disulfide, and the like. By combining the hardener composition for an epoxy resin of the present invention and the polyepoxy compound (A), a one-liquid type heat-curable epoxy resin composition can be provided. As the polyepoxy compound of the component (A) used in the present invention, for example, a polyglycidyl ether compound which may be a mononuclear polyphenol compound such as p-benzene phenol, resorcin, catechol or phloroglucin. Dicarboxylate, bisphenol, methylene-----------^-----------------------^9 (Please read the note on the back first) Please fill out this page again) -11 A7

1248448 V. INSTRUCTIONS (9) Bisphenol (bisphenol F), methylene bis(o-cresol), ethylene bisphenol, sub-isoendyl double (double A), isopropylidene double (o-toluene test), four desert bases A, 1,3-bis(4-hydroxycumylbenzene), M_double (renine cumene bromide), 1,1,3 - two ( 4-3⁄4 phenyl)butane, i,l,2,2-tetrakis(4-polyphenylene)ethane, thiobisphenol, sulfonate bisphenol, hydroxybisphenol, phenolic phenolic resin , polyphenolic resin of o-cresol, ethyl phenyl phenolic resin, butyl phenyl acid resin, octyl phenyl phenolic resin, phenolic resin of resorcinol, polynuclear polyphenol compound such as indophenol Glyceryl ether compound; ethanol, propanol, butanol, hexanediol, polyol, thiol, glycerol, trimethylpropane, pentaerythritol, sorbitol, bisphenol A _ ethylene oxide plus a polyglycidyl ether of a polyhydric alcohol such as a compound; maleic acid, butyric acid, methylene succinic acid, succinic acid, glutaric acid, suberic acid, bismuth adipic acid , one version, polyacid, trimer acid Phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylene tetrahydrogen a homopolymer or copolymer of glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as phthalic acid and glycidyl methacrylate; N, N• diglycidyl aniline, bis (4-( An epoxy compound having a glycidylamino group such as N-methyl_N_glycidylamino)phenyl)methane or the like. In the present invention, 0.1 to 200 parts by weight of the hardener composition for an epoxy resin of the present invention is used per 1 part by weight of the polyepoxy compound (A), and preferably 1 to 1 weight is used. In the range of parts, if the amount p is more than the parts by weight, there is a possibility that the curability is not obtained, and in the case of more than 2 parts by weight, the P is lower than the physical properties of the cured material, so it is not Good. -12- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -----------Install--------Set------- --^9 (Please read the note on the back and then fill out this page) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1248448 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing A7 V. Invention Description (1〇) In the present invention In the curable epoxy resin composition, in addition to the (B) component and the component (c) component hardener, a generally known hardener for an epoxy resin may be used in combination. The hardening agent may be a polyamine as exemplified as the above (e) component, or may be phenylglycidyl ether, butyl glycidyl ether, bisphenol A _ glycidyl ether, or the like in a usual manner. a polyepoxy addition-modified material obtained by reacting various epoxy resins such as hydrarginyl ethers such as phenol F _ glycidyl ether or glycidyl esters of carboxylic acid; and organic polyamines obtained by a usual method An amidated modified product obtained by reacting with an acid such as phthalic acid, isophthalic acid 35 or di(tetra); and such a polyamine and aldehyde such as formaldehyde and phenol, cresol, and the like are used in a usual manner. The cresol, the third butyl phenol, and the resorcinol are equal to the mannitol modified product obtained by the phenol reaction having at least one hydroformylation reactive site in the core. Further, a latent hardening agent such as dicyanodiamine, melamine guanamine, acid anhydride, dicarboxylic acid dioxane or imidazole may also be used. In addition, in the case of using the epoxy resin composition of the present invention as a coating or an adhesive, in order to facilitate the treatment, it is usually a solvent, such as methyl ethyl ketone or methyl amyl ketone. , [Ethyl ketone, acetone, methyl isopropyl hydrazine, propylene glycol monomethyl ether acetate hydrazine, cyclohexanium equivalent 酉 similar; four & ^ South, 1,2-methoxy methoxy, u• Ethers such as diethoxyethane; ethers such as ethyl acetonitrile and n-butyl acetate; ethers such as propylene glycol monomethyl ether acetate: :iso- or n-butanol, iso- or n-propanol, pentane Alcohols such as alcohol; aromatic hydrocarbons such as benzene, methyl:, xylene; decanediol oil, D, diene, hydrazine, etc.; 矿ffe; mineral oil, silk wazelu #31G (Kesmore Mountain oil (Shares)), Thorubesud (Yakesson Chemical Co., Ltd.) and other terpene hydrocarbon solvents; tetrachlorinated-13- (cnS)A4 _Specifications (10) x 297 mm) --Book --------- (Please read the notes on the back and fill out this page) 1248448 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 V. Invention description (11 carbon, gas, three gas Ethylene, methylene chloride Self-chemically aliphatic hydrocarbon; halogenated aromatic benzene such as gasified benzene; aniline, triethylamine, yttrium, sinter, acetic acid, sulphuric acid, carbon disulfide, etc. Further, in the epoxy resin composition of the present invention, It may also contain a hardening catalyst as needed; a mono-glycidyl ether, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, coal char, etc. Reactive or non-reactive diluent (plasticizer) Fillers or pigments such as glass fiber, carbon fiber, cellulose, strontium sand, cement, kaolin, clay, hydroxide, bentonite, talc, ♦ oxygen, micro-powder oxygen, titanium dioxide, carbon black, graphite, iron oxide, asphalt; Thickener; thixotropic agent; flame retardant; defoamer; rust inhibitor; 'colloidal oxime, colloidal aluminum oxide and other commonly used additives, can also be used together with xylene resin, petroleum resin and other adhesive resin The curable epoxy resin composition of the present invention can be used, for example, as a coating or an adhesive for concrete, cement paste, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc. Adhesive Frozen food labels, release labels, P0S labels, adhesive wallpapers, adhesives for flooring materials; fine paper, lightweight coated paper, shovel-based paper, coated paper, carbonless photocopying machines, impregnated paper, etc. ; Tianzhu eight fear fiber, synthetic weiwei, glass fiber, carbon fiber, etc.

K tanning agent, processing agent I fiber treatment agent; bottom sealing machine, lacquer primer and other steam watch / flying soap use; sealing materials, cement mixture, waterproof materials and other building materials, etc., τ is especially suitable for As a coating for various substrates, next. The following examples are disclosed to explain the present invention in a more detailed manner, but the present invention is not limited thereto. -14- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ------------ φ Μ-------- order----- -------^9 (Please read the note on the back? Please fill out this page again) 1248448 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 ---------- -B7____ V. (Description of the Invention) (12) [Manufacturing Example 1] (The hardener composition of Example 1-1) Into 162.5 g of isobutanol, 162 5 g of xylene, 2 4 g (2 mol) of N, N_ Dimethylaminopropylamine, 87 g (〇5 mol) of diammonium diacetate, and 85 g (0.5 mol) of isophorone diamine, at 6〇~7〇χ: Mix and stir for 30 minutes. To the solution was 6 6 6 g (2 mol) of isophorone diisocyanate in a 67 wt% xylene solution. After the completion of the dropwise addition, the temperature was raised, and the mixture was aged at 140 to 150 C for 2 hours, and the absorption of 2250 cm/m of the isocyanate absorption was confirmed by IR, and the temperature was raised to 2 Torr, and the temperature was increased for 2 hours. The solvent was removed by pressure, and the solvent was decompressed under reduced pressure for 1 hour at i9〇~2〇〇°c, 5〇~6〇mmHg to obtain a pale white solid substance. [Production Examples 2 to 11] (Examples 1-2 to 1-10 and Comparative Example i _ 丨 hardener composition) The compositions shown in Tables 1 to 3 were blended, and a curing agent composition was produced according to Production Example 1. [Manufacturing Example 1 2 ] (hardener composition of Examples 1 to 11) 162.5 g of isobutanol, 162.5 g of xylene, and 204 g (2 mol) of N,N-dimethylaminopropylamine were charged. 87 g (〇5 mol) of diammonium adipate, and 85 g (0.5 mol) of isophorone diamine, at 6〇~7〇. Mix underarm and stir for 30 minutes. A solution of 666 g (2 mol) of isophorone diisocyanate in 67 wt% xylene was added dropwise thereto. After the completion of the dropwise addition, the temperature was raised, and the mixture was aged at 140 to 150 ° C for 2 hours, and the absorption of 2250 cm -1 of the isocyanate absorption was confirmed to disappear, and 16 g (1 mol) was charged. 15- The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------------Installation--------Set------- --^9 (Please read the note on the back and then fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1248448 A7 -------B7 _ V. Invention Description (13) Hexamethylenediamine 2,4 g (2 mol) of dimethylaminopropylamine, mixed and stirred at 12 (rc) for 30 minutes. Slowly drip 540 g (2 mol) of diglycidyl ortho Toluidine. After the dropwise addition, the mixture was refluxed at 14045 ° C for 2 hours, and then heated to 200 ° C. The solvent was removed at room temperature for 2 hours, and then at 190 to 200 ° C, 50 to 60 mm. The solvent was decompressed under a mercury column for 1 hour to obtain a pale white solid resin. [Production Examples 13 to 15] (Example 1 - 12 to 1 - 14 hardener composition) , according to Production Example 1 1 to manufacture a hardener [Manufacturing Example 1 6 ] (hardener composition of Examples 1 to 15) 162.5 g of isobutanol, 162.5 g of xylene, and 408 g (4 mol) of N,N-methylamine were charged. Propylamine, 174 g (1 mol) of diammonium adipate, and 170 g (1 mol) of isophorone diamine at 6 Torr to 7 Torr. (: Mix under stirring for 30 minutes. 486 g (1β8 mol) of diglycidyl o-toluidine (epoxy equivalent weight: 135) and 4 g of glycidyl m-xylene diamine were sequentially added thereto. (Ethylene equivalent is 丨〇〇), refluxing for 2 hours, into which 6 6 6 g (2 mol) of isophorone diisocyanate 67 wt% xylene solution was added dropwise. After that, the temperature was raised to 140 to 150 ° C, and the mixture was refluxed for 2 hours. The absorption of 2250 cm -1 of the isocyanate absorption was confirmed to disappear, and the temperature was raised to 2 ° C until 2 hours of atmospheric pressure desolvation. Then, the solvent was decompressed under reduced pressure for 1 hour at 19 Torr to 2 〇〇 ° C, 5 Torr to 60 mm Hg to obtain a pale white solid material. [Manufacturing Example 17 to 20] -16- Zhang scale applies China National Standard (CNS) A4 specification (21〇x 297 mm) (Please read the note on the back and fill in this page) 装装--------订------- --Line Thai Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1248448 A7 ____Β7_ V. Invention Description (14) (Examples 16 to 1-18 and Comparative Example ι_2 hardener composition) Blending Table 3 'According to Production Example 1 to produce a hardener composition. [Production Example 2 1] (The hardener composition of Examples 1 to 19) was charged with 202 g of one toluene, 75.4 g (0.65 mol) of hexamethylenediamine, and 132.6 g (1.3 mol) of dimethyl Glycosylamine, at 12 〇. Mix the hem under the mix for 30 minutes. 26 g (0.065 mol) of tetraglycidyl-m-xylylenediamine (epoxy equivalent oxime) was added dropwise thereto, and refluxed for 3 hours, and 570 g (2.10 mol) was added thereto. The bisglycidyl o-toluidine (epoxy equivalent of 135) was refluxed for 3 hours to obtain a brownish brown liquid (polyamine epoxy adduct) having an active hydrogen equivalent of 1350. 888 g of xylene and 204 g (2 mol) of dimethylaminopropylamine were charged and stirred and mixed at 80 C for 3 minutes. Thereto was added dropwise 666 g (2 mol) of isophorone diisocyanate to 67 weight. / 〇 xylene solution, refluxing at 1 〇〇 °c for 1 hour, then slowly add 4 7 4 g (丨莫耳) of adipic acid dioxime, down at 13 ° ° C for 3 hours The reflux is ripe. The absorption of 2250 cm-1, which was confirmed to be absorbed by isodecanoate at 151, has disappeared. 4 6 2 g of the above-prepared polyamine epoxy adduct was charged therein, and the mixture was stirred at 13 (TC) to raise the temperature to 200 ° C, and the solvent was removed at room temperature for 2 hours, and then at 190 to 200 C. The solvent was decompressed under reduced pressure for 1 hour at 50 to 60 φ mHg to obtain a pale yellow solid material. [Experimental Example] The following tests were carried out on the compositions shown in Tables 1 to 3. (Sclerosing) • 17- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -----------Install--------Set--------- ( Please read the notes on the back and fill out this page.) 1248448 A7 B7 V. INSTRUCTIONS (15) Mix Adika resin Ep_49〇1E at a ratio of 100/20 (Asahi Chemical Industry Co., Ltd. (monthly) k, double F type Epoxy resin) and hardener composition, using a gelation tester to test the object suspended on the 3 rolls. The time when the wire can no longer be pulled is judged as the gelation time. (Stability) 100/20 The ratio of the Adika resin eP_49〇1e and the hardener composition was mixed, and the material suspended on the 3 rolls was allowed to stand at 25 ° C for 3 hours, and then the viscosity at 25 C was determined as the initial viscosity. Long-term viscosity (P: poise) placed under * under the armpit. (Tensile test) Adhesive resin Ep_49〇1E and hardener composition are mixed at a ratio of 100/20, using the object suspended on the 3 rolls, The soft steel plate SPCC-SD (1.6 mm X 25 mm X 1 mm) manufactured by Japan's test panel is made into a 25 mm X 10 mm pasting place, and the above is posted on it, and heated at l5 (rc for 1 hour). Then, the shearing force (kg/cm2) was measured at a test speed of 50 mm/min at 23 ° C. (Tear test) Adhesive resin EP-mixed at a ratio of 100/20 4901E and hardener composition, using the material suspended from the 3 rolls, the soft steel plate SPCC-SD (1.6 mm X 15 mm X 100 mm) made by the Japanese test plate is made into a 25 mm X 1 mm mark. The above objects were posted on it at i 5 〇. (: heating for 1 hour followed by 2 minutes at 2 3 ° C, measured at a test speed of 200 mm / min. Square centimeter) (softening point) -18- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) (please Read the notes on the back and fill out this page) _装--------Book---- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1248448 A7 ___ B7 ____ V. Invention Description (16) to 100/ At a ratio of 20, Adika resin EP-4901E and a hardener composition were mixed and measured using a softening point measuring machine (manufactured by Meihu Co., Ltd.). (Glass Transfer Point) The Adika resin EP-4901E and the hardener composition were mixed at a ratio of 100/20, and were measured using a differential calorimeter (successful electronic manufacturing) using a material suspended from the three rolls. The measurement conditions were: 100. (:/min rate is raised to 15 〇QC, kept at 150C for 1 hour, cooled at i〇〇°c/min, and after 5 sec cooling, at a rate of 5 °C/min To 2 〇0 °c. Obtain the glass transition point from the bending point. -----------Install--------Book---------^ 9 (Please read the phonetic transcription on the back? Please fill out this page again) Printed by the Intellectual Property Office of the Ministry of Economic Affairs

1248448 A7 B7 V. INSTRUCTIONS (17) Table 1 Hardener Composition Examples 1-1 1-2 1-3 1-4 1-5 1-6 1-7 ADH 87 174 87 87 70 113 87 Isophorone Diamine 85 m-xylenediamine 68 Hexamethylenediamine 58 46 75 58 1,2-diaminopropane dimethylamine propylamine 204 204 204 204 245 143 204 GOT TETRAD Isophorone isocyanate 666 666 666 666 666 666 533 1,3-BIC TDI Isophoronediamine hexamethylenediamine dimethylamine propylamine TETRAD GOT Yadi Kaleijin EP-4100 Evaluation of hardenability (minutes) ~8〇T: 32 60< 31 29 31 29 28 100U 5 60 < 4 5 7 2 1 120U < 0.5 60 << 0.5 < 0.5 < 0.5 < 0.5 < 0.5 150 ϋ < 0.5 < 0.5 < 0.5 < 0.5 <0.5 <0.5 <0.5 Stability (Ρ/251;) Initial 80 75 82 81 74 86 84 40X; X7 Day 89 80 92 86 79 92 101 40X; X 14 Day 122 108 124 119 99 128 139 Shear Stress 224 215 221 218 224 230 229 Tear test 1.95 1.90 1.95 1.95 1.95 1.99 1.98 Softening point 145 149 142 141 145 150 148 Glass transfer point 91 95 91 90 91 93 93 (Please read the note on the back and fill out this page) Department of Economics Intellectual Property Office Staff Cooperatives Printed ADH: Dibenzoate肼1,3-BIC : 67% methyl solution of 1,3-bisisocyanate methylcyclohexane TDI : tolyl group; 67% toluene solution of isocyanate GOT : diglycidyl o-toluidine TETRAD : tetraglycidyl Inter-xylylenediamine sub-dicarbene EP-4100: Asahi Industrial Co., Ltd., bisphenol A epoxy resin-20- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 PCT) 1248448 A7 B7 V. INSTRUCTIONS (18) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printed Table 2 Hardener Composition Example 1-8 1-9 1-10 Ml 1-12 1-13 1-14 ADH 87 87 87 87 87 87 87 Isophoronediamine 85 85 85 85 85 m-xylenediamine hexamethylenediamine 58 1,2-diaminopropane 37 Dimethylaminopropylamine 204 204 204 204 204 204 204 GOT TETRAD Isophorone Isocyanate 666 666 666 666 666 1,3-B IC 582 TDI 522 Isophoronediamine 170 Hexamethylenediamine 116 116 116 Dimethylaminopropylamine 204 204 204 204 TETRAD GOT 540 540 540 Yadikaleijin EP-4100 760 Evaluation of hardenability (minutes) 80°C 32 32 15 10 10 10 10 100°C 6 2 1 1 1 1 1 120°C - <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 Stability (P/ 25°C) Initial 81 80 84 75 74 76 78 40°C X7EJ 91 95 91 90 88 91 93 40〇C X14 Day 128 134 136 135 132 134 131 Shear stress 223 222 216 213 212 216 220 Tear test 1.93 1.90 1.92 1.83 1.82 1.89 1.90 Softening point 145 143 140 115 113 121 119 Glass transfer point 90 91 91 89 90 89 90 -21 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------ -----^-装--------Book--------- (Please read the notes on the back and fill out this page) 1248448 A7 B7 V. Description of invention (19) Economy Ministry of Intellectual Property Office Staff Consumer Cooperatives Printed Table 3 Hardener Composition Examples Comparative Example 1-15 1-16 1-17 1-18 1-19 1-1 1-21 ADH 174 174 174 174 174 Isophoronediamine 170 170 170 340 m-xylenediamine 136 Hexamethylenediamine 116 1,2-diaminopropane dimethylamine propylamine 408 408 408 408 204 204 408 GOT 486 486 486 486 486 TETRAD 40 40 40 40 40 Isophorone isocyanate 666 666 666 666 666 666 1,3-BIC 582 TDI Isophoronediamine Hexamethylenediamine 35 Dimethylaminopropylamine 61 TETRAD 12 GOT 400 Yadi Kaleijin EP-4100 Evaluation of hardenability 80 °C 10 10 10 10 10 30 10 100 °C 1 1 1 1 1 2 1 120 °C <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 Stability (P/25 ° C) Initial 77 77 76 75 75 90 90 40〇C X7 89 95 93 92 90 GEL GEL 40°C xl4 Day _ 127 130 130 128 125 — — Shear stress 213 219 215 210 212 210 213 Tear test 1.83 1.83 1.83 1.87 1.87 1.53 1.47 Softening point 117 121 120 113 110 105 101 Glass transfer point 89 89 89 89 89 88 85 -22 - This paper scale applies to Chinese national standards ( CNS) A4 Specifications 210 X 297 mm) -----------^vi --------Book·------- (Please read the notes on the back and fill out this page) 1248448 A7 B7 V. INSTRUCTIONS (2〇) It is clear from the examples that it contains polyepoxy compounds, reacted with N,N•dialkylamine alkylamine, dicarboxylic acid diterpene and organic polyisocyanate. The epoxy resin composition of the hardener has excellent storage stability under the single-liquid hardening system, and the curing speed is fast, and the physical properties of the obtained cured product are also good. By

The balance of these can be adjusted by using other amine compounds or epoxy compounds in these ingredients. I, in contrast, the hardening agent obtained by reacting a polyamine and a general polyisocyanate which are commonly used, such as N,N-dialkylamine alkylamine and isophorone diamine, can be hardened. A good thing, but only the thing that preserves the stability of Yang sound. (Please read the notes on the back and fill out this page again) Binding---------Φ. Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed 23- Public Book 1248448 Application for the Period of the Case _089127178 Category A4 C4 Chinese Speaking Page (October 91) Inventive i New 4th specification, Mo 3 name Chinese hardener composition and hardenable epoxy resin composition English-, invention + creator

CURING AGENT COMPOSITION AND CURING EPOXY RESIN COMPOSITION Name 1. Ogawa Akira 2. Abe School of Nationality Residence, Residence 1.-2. Both of Japan's equipment 1. Japan's Saitama Prefecture, Nanjo-Yu-gun, Shibu-machi, Showauma, 2, Fandi, Xujiu Electrochemical Industry Co., Ltd. In the company's order, the applicant's surname is the name of the applicant. (Name f Nationality Risho Asahi Chemical Industry Co., Ltd. ASAHI DENKA KOGYO KABUSHIKI KAISHA 曰本线日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本 日本Nakajima Hiroshi, the paper size of the Nakajima, the Aokawa, Arakawa, Arakawa, Tokyo, Aug. 3, A4 specification (η〇χ 297 mm)

Claims (1)

1248 Today 4[^9127128 Patent Application As Chinese Application for Patent Renewal (November 1994) Supervisor: ---- D8' VI. Application Special #^~ " ---- 1. Species of oxygen A resin hardener composition characterized by comprising a reactant (B) which comprises: a monoamine compound (a) comprising an amine compound of the general formula (I); and a relative component (a) Moer, which is a polyamine compound (b) containing dicarboxylic acid di-SS month well, which may be selected from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and Aminopropane, hydrazine, 2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine, m-xylenediamine, diamine a compound of the group consisting of diphenylmethane, diaminodiphenyl hydrazine, pyridazine and hexamethylene T diamine; selected from the group consisting of 1,3-bisisocyanate methylcyclohexane, 2, wood tolyl diisocyanate Stuffed, 2,6-streptyldiisocyanate, 4,4,diphenylmethane diisocyanate, phenyl diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, tetra-strand Diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, hydrazine, 4_cyclohexyl diisocyanate, 4,4,-dicyclohexylmethane diisocyanate, 3,3, dimethoxy- 4,4,-bis-phenylene diisocyanate, i,5-extended diisocyanate, 1,5-tetrahydroindenyl diisocyanate, isophorone diisocyanate relative to one of (a) and (b) The amine group of the amine compound 'NCO group uses 0.1 to 2 organic polyisocyanates (c); (I) 68355-94ii01.DOC This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1248448 A8 B8 C8 In the scope of patent clearing, ^^ and Han are respectively carbon number i The alkyl group of ～8 or the combination of h and R2 is a stretching group which may contain an oxygen atom or a nitrogen atom, and n is 1 to 6 〇2. A hardener composition for an epoxy resin according to the first aspect of the patent application, wherein the compound A, bisphenol F, diglycidylaniline, diglycidyl o-toluidine, phenyl glycidyl ether, toluene The glycidyl group, the butyl phenyl glycidyl ether, the tetraglycidyl metaxylene diamine, the amine compound iNH2 group of the (a) and (b), and the epoxy group using 0.99 The following epoxy compound (d) is used for the reaction. 3. The hardener composition for epoxy resin according to the scope of claim 2 or wherein the amine compound (a) of the general formula (I) is dimethylaminopropylamine. The hardener composition for an epoxy resin according to item i or item 2 of the patent application, wherein the far acid is diacid acid is adipic acid. 5. The hardener composition for epoxy resins according to claim 2 or 2, wherein the polyamine compound (b) is used in combination with isophorone diamine, m-xylylenediamine and hexamethylene At least one of the amines. A hardener composition for an epoxy resin according to claim 5, wherein the diuronic acid dioxime is used in an amount of 5 mol or less selected from the group consisting of isophorone diamine and methylene diacetate. At least one amine compound of toluenediamine and hexamethylenediamine. 7. The hardener composition for epoxy resin according to the scope of claim 2 or 2, wherein the organic polyisocyanate (c) is selected from the group consisting of isophorone diisocyanide-2-68355-941101.DOC This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) —---------- 1248448 Patent application scope 至少 At least one of 1,3-bis-cyanate methyl ring or tolyl diisocyanate. 8·T According to the patent application scope 丨 or 2 of the epoxy resin hardener combination\ wherein the oxime compound (d) is selected from the group consisting of tetra-brown glyceryl-m-xylene-amine, diglycidyl o-toluidine At least one of them. 9· f According to the patent application scope [or] of the epoxy resin hardener combination sentence, which comprises the reactant (B) and the epoxy compound (C) of the amine compound. 10. The hardener composition for an epoxy resin according to claim 9, wherein the amine compound (4) which provides the epoxy adduct (c) of the amine compound comprises the above-mentioned general formula (amine) amine compound. According to the patent scope, the epoxy resin hardener combination is provided, wherein the amine compound (e) which provides the epoxy compound (c) of the amine compound is selected from the group consisting of isophorone diamine and diammonium. A composition of at least one of toluenediamine and hexamethylenediamine. The hardener composition for epoxy resin according to claim 9 of the patent application, and the epoxy compound (1) which provides the epoxy adduct (C) of the amine compound is selected from the group consisting of tetraglycidyl-diphenyl- ^ At least one of 丫丰一妆, diglycidyl amenine. 13. The epoxy resin hardener composition according to item 9 of the patent scope, wherein: an epoxy of 0.5 to 2% oxygen compound (f) is used with respect to one amine compound (4) base. M. - Single-component heat-curing epoxy resin composition, 1 series of each polyoxyl compound (A) and any one of the patent application pages (1); 68355-941101.DOC 1248448 A8 B8 C8 D8 硬化, the patented range of hardener compositions for epoxy resins. 68355-941 101.DOC - 4 - This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm)